Perovskite-like Oxides Research Articles

Photocatalytic Hydrogen Production from Aqueous Solutions of Glucose and Xylose over Layered Perovskite-like Oxides HCa2Nb3O10, H2La2Ti3O10 and Their Inorganic-Organic Derivatives.

Nowadays, the efficient conversion of plant biomass components (alcohols, carbohydrates, etc.) into more energy-intensive fuels, such as hydrogen, is one of the urgent scientific and technological problems. The present study is the first one focused on the photoinduced hydrogen evolution from aqueous D-glucose and D-xylose using layered perovskite-like oxides HCa2Nb3O10, H2La2Ti3O10, and their organically modified derivatives that have previously proven themselves as highly active photocatalysts. The photocatalytic performance was investigated for the bare compounds and products of their surface modification with a 1 mass. % Pt cocatalyst. The photocatalytic experiments followed an innovative scheme including dark stages as well as the control of the reaction suspension’s pH and composition. The study has revealed that the inorganic−organic derivatives of the layered perovskite-like oxides can provide efficient conversion of carbohydrates into hydrogen fuel, being up to 8.3 times more active than the unmodified materials and reaching apparent quantum efficiency of 8.8%. Based on new and previously obtained data, it was shown that the oxides’ interlayer space functions as an additional reaction zone in the photocatalytic hydrogen production and the contribution of this zone to the overall activity is dependent on the steric characteristics of the sacrificial agent used.

Oxygen-Deficient (Ln,Sr)2NiO4- δ Nickelates for Oxygen Electrodes of Solid Oxide Fuel and Electrolysis Cells: Anisotropic Thermochemical Expansion and Thermomechanical Constraints

Perovskite-like and perovskite-related oxides based on variable-valence transition metals may exhibit substantial changes in oxygen content in the course of temperature cycling or under variation of oxygen chemical potential at elevated temperatures. This gives rise to a chemical contribution to the thermal expansion (chemical expansion/contraction or chemical strain) originating mainly from the accompanying changes in the average oxidation state of transition metal cations and, consequently, their ionic radii. Excessive dimensional changes caused by the chemical expansion impose constraints on the applicability of functional oxides at elevated temperatures and under variable redox conditions (due to thermomechanical instability or incompatibility with other materials) and complicate the processing of oxide ceramics at high temperatures. Another unfavorable phenomenon is microcracking caused by a strongly anisotropic expansion of crystal lattice, with effects on the microstructural and mechanical integrity and electrical and electrochemical properties. The present work is a representative study case that focuses on layered Ln2NiO4-based ceramic materials for oxygen electrodes of solid oxide fuel/electrolysis cells (SOFC/SOEC).Ln2NiO4+δ–based oxides (Ln = La, Pr, Nd) with perovskite-related K2NiF4-type structure demonstrate high oxygen diffusivity and surface exchange kinetics in combination with comparatively high electronic conductivity and are considered, therefore, as attractive mixed ionic-electronic conductors for oxygen electrodes of high-temperature SOFC/SOEC [1]. Acceptor-type substitution of Ln3+ by Sr2+ in Ln2NiO4+ δ is compensated by comparatively high oxygen deficiency in Sr-rich Ln2-xSrxNiO4-δ phases at elevated temperatures [2,3]. The transition from oxygen excess to oxygen deficiency is expected to be accompanied by a change in the ionic transport mechanism from prevailing interstitial oxygen diffusion in rock-salt layers to oxygen vacancy diffusion in perovskite-type layers.Ceramic powders of Ln2-xSrxNiO4-δ (Ln = La, Nd, Pr, x = 1.0-1.6) were prepared by the Pechini method with final calcination steps at 1150-1200°C in oxygen. Thermogravimetric studies confirmed that acceptor-type substitution by strontium is compensated by the formation of oxygen vacancies and electron-holes and progressively increases high-temperature oxygen nonstoichiometry (Fig.1A), which reaches as high as δ = 0.36-0.40 for x = 1.6 at 900°C in air. High-temperature XRD studies demonstrated that Ln2-xSrxNiO4-δ nickelates exhibit strongly anisotropic lattice expansion interrelated with oxygen deficiency changes on heating (Fig.1B). Highly anisotropic expansion induces microcracking phenomenon, which, in turn, results in a strong hysteresis in dimensional changes (Fig.1C) and also in variations of electrical conductivity (Fig.1D) on cycling in air for the ceramic samples sintered at 1200-1300°C.An appropriate approach to minimize or neglect the undesirable effects of anisotropic expansion and microcracking is to preserve the grain size in Ln2-xSrxNiO4-δ ceramics or porous electrodes at ~1 micron or submicron level. In particular, spark plasma sintering with subsequent careful oxidation treatment was adopted to avoid grain growth and to produce mechanically stable ceramics with smooth reversible thermochemical expansion and enhanced electrical properties. Acknowledgments: This work was supported by the FCT/MCTES/FEDER (projects CARBOSTEAM (POCI-01-0145-FEDER-032295) and CICECO-Aveiro Institute of Materials (UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020), and PhD grant SFRH/BD/138773/2018).

Approach to the Characterization of Monolithic Catalysts Based on La Perovskite-like Oxides and Their Application for VOC Oxidation under Simulated Indoor Environment Conditions

Catalysts are very important in controlling the pollutant emissions and are used for hundreds of chemical processes. Currently, noble metal-based catalysts are being replaced for other kinds of materials. In this study, three lanthanum-based perovskite-like oxides were synthesized (LaCo, LaCoMn, and LaMn) by the glycine-combustion method. The powder catalysts obtained were supported onto cordierite ceramic monoliths using an optimized washcoating methodology to obtain the subsequent monolithic catalysts (LaCo-S, LaCoMn-S, and LaMn-S). Sample characterization confirmed the formation of the perovskite-like phase in the powder materials as well as the presence of the perovskite phase after supporting it onto the monolithic structure. The XPS analysis showed a general decrease in lattice oxygen species for monolithic catalysts, mainly caused by the colloidal silica used as a binder agent during the washcoating process. Additionally, some variations in the oxidation state distribution for elements in Co-containing systems suggest a stronger interaction between cordierite and such catalysts. The catalytic activity results indicated that powder and monolithic catalysts were active for single-component VOC oxidation in the following order: 2-propanol > n-hexane ≅ mixture > toluene, and there was no evidence of loss of catalytic activity after supporting the catalysts. However, LaMn-S had a better catalytic performance for all VOC tested under dry conditions, achieving oxidation temperatures between 230–420 °C. The oxidation efficiency for the VOC mixture was strongly affected by the presence of moisture linking the oxidation efficiency at wet conditions to the VOC chemical nature. Additionally, for higher VOC concentrations, the catalyst efficiency decreased due to the limited number of active sites.

The Structural and Dielectric Properties of Bi3−xNdxTi1.5W0.5O9 (x = 0.25, 0.5, 0.75, 1.0)

A new series of layered perovskite-like oxides Bi3−xNdxTi1.5W0.5O9 (x = 0.25, 0.5, 0.75, 1.0) was synthesized by the method of high-temperature solid-state reaction, in which partial substitution of bismuth (Bi) atoms in the dodecahedra of the perovskite layer (A-positions) by Nd atoms takes place. X-ray structural studies have shown that all compounds are single-phase and have the structure of Aurivillius phases (APs), with close parameters of orthorhombic unit cells corresponding to space group A21am. The dependences of the relative permittivity ε/ε0 and the tangent of loss tgσ at different frequencies on temperature were measured. The piezoelectric constant d33 was measured for Bi3−xNdxTi1.5W0.5O9 (x = 0.25, 0.5, 0.75) compounds of the synthesized series.

Crystal structure, microstructure, piezoelectric and dielectric properties of high-temperature piezoceramics Bi-=SUB=-3-x-=/SUB=-Nd-=SUB=-x-=/SUB=-Ti-=SUB=-1.5-=/SUB=-W-=SUB=-0.5-=/SUB=-O-=SUB=-9-=/SUB=- (x=0, 0.1, 0.2)

A new series of perovskite-like oxides Bi3-xNdxTi1.5W0.5O9 (x=0, 0.1, 0.2) has been synthesized by the method of high-temperature solid-state reaction. The X-ray diffraction study showed that the compounds are single-phase and have the structure of the family of Aurivillius phases with parameters close to the orthorhombic unit cell corresponding to the space group A21am. The relative permittivity ε/ε0 and loss angle tangent tgsigma are measured as functions of temperature at different frequencies. The piezoelectric modulus d33 was measured for the synthesized compounds. The microstructure of Bi3-xNdxTi1.5W0.5O9 (x=0, 0.1, 0.2) was obtained. The study of the microstructure shows that the crystallites have a shape characteristic of Aurivillius phases. Keywords: Aurivillius phases, Bi2.8Nd0.2Ti1.5W0.5O9, activation energy Ea, Curie temperature TC.

Structural and Dielectric Properties of Bi-=SUB=-3-=/SUB=-Ti-=SUB=-1.5-=/SUB=-W-=SUB=-0.5-=/SUB=-O-=SUB=-9-=/SUB=-

Layered perovskite-like oxide Bi3Ti1.5W0.5O9 has been synthesized by the method of high-temperature solid-state reaction. The X-ray diffraction study showed that the compound is single-phase and has the structure of the family of Aurivillius phases (AP) with parameters close to the orthorhombic unit cell corresponding to the space group A21am. The temperature dependences of the relative permittivity ε/ε0 and the loss tangent tgsigma are measured at different frequencies. For the synthesized compound, the piezoelectric modulus d33 was measured. The microstructure of Bi3Ti1.5W0.5O9 has been obtained. Keywords: Aurivillius phases, Bi3Ti1.5W0.5O9, activation energy Ea, Curie temperature TC, piezoelectric modulus d33.

SEARCH FOR WAYS OF CONTROLLED MODIFICATION OF CHARACTERISTICS OF FUNCTIONAL UNITS OF ADAPTIVE AIR PURIFICATION SYSTEMS

Information on alkaline coordination nitrates of rare-earth elements of the cerium subgroup - precursors of promising modern multifunctional materials - on the conditions of their formation and existence, the nature of the chemical bond, the composition, structure, shape of the Ln coordination polyhedra, the type of ligand coordination, and the existence of isotypic series in stoichiometry are generalized. composition, structure, characteristic properties. The data obtained (as primary information) is the basis for the detection, identification, and control of the phase state of processing objects in the preparatory stages, the choice of criteria for the compatibility of the components in the formation of single-layer and layered nanostructured oxide composite systems of lanthanides and transition elements for general purposes, with catalytic and photocatalytic activity, coatings self-cleaning with hydrophilic properties; development of various combined methods for their activation and identification of technological functional dependencies; controlled modification of the properties of the obtained target products. To increase the photocatalytic activity of coating samples based on highly dispersed anatase TiO2, a methodology for chemical modification of oxidation centers in their surface layer with heat treatment in contact with thermolysis products of alkaline coordination lanthanide nitrate melts is proposed. An effective test photocatalytic destruction of organic substrates vapors has been discovered using ethanol as an example.Effective activation of the functioning of functional units in the composition of self-adjusting air purification complexes using new photocatalytically active three-layer perovskite-like oxide materials M2Ln2Ti3O10 (M - Li, Na, K; Ln - La, Nd) has been proven. The variability of such methods for creating and modifying the characteristics of polyfunctional coatings is determined by the number and individual properties of representatives of the natural series of lanthanides, alkali metals of the periodic system, the peculiarities of their cooperative behavior in the preparatory technological stages, conditions and methods of activation of formation processes, the nature of the substrate, and other factors.

Synthesis and thermal behavior of nanoceramic material based on Bi<sub>13</sub>Fe<sub>5</sub>Ti<sub>6</sub>O<sub>39</sub>

The process of formation by the chemical coprecipitation method of nanoceramic material based on layered perovskite-like complex oxide Bi13Fe5Ti6O39 with the structure of the Aurivillius phase has been described. The temperatures of the onset of formation, the onset of decomposition, and activation of sintering, as well as the coefficient of linear thermal extension of the material, have been determined. Technological parameters for the synthesis of the material with a high yield of the target product and the ability to vary the crystallite size in the range of 70‒85 nm have been determined.

Physical-Chemical Exfoliation of n-Alkylamine Derivatives of Layered Perovskite-like Oxide H2K0.5Bi2.5Ti4O13 into Nanosheets.

In the present work, we report the results on exfoliation and coating formation of inorganic–organic hybrids based on the layered perovskite-like bismuth titanate H2K0.5Bi2.5Ti4O13·H2O that could be prepared by a simple ion exchange reaction from a Ruddlesden–Popper phase K2.5Bi2.5Ti4O13. The inorganic–organic hybrids were synthesized by intercalation reactions. Exfoliation into nanosheets was performed for the starting hydrated protonated titanate and for the derivatives intercalated by n-alkylamines to study the influence of preliminary intercalation on exfoliation efficiency. The selected precursors were exfoliated in aqueous solutions of tetrabutylammonium hydroxide using facile stirring and ultrasonication. The suspensions of nanosheets obtained were characterized using UV–vis spectrophotometry, dynamic light scattering, inductively coupled plasma spectroscopy, and gravimetry. Nanosheets were coated on preliminarily polyethyleneimine-covered Si substrates using a self-assembly procedure and studied using atomic force and scanning electron microscopy.

1H NMR Study of the HCa2Nb3O10 Photocatalyst with Different Hydration Levels.

The photocatalytic activity of layered perovskite-like oxides in water splitting reaction is dependent on the hydration level and species located in the interlayer slab: simple or complex cations as well as hydrogen-bonded or non-hydrogen-bonded H2O. To study proton localization and dynamics in the HCa2Nb3O10·yH2O photocatalyst with different hydration levels (hydrated—α-form, dehydrated—γ-form, and intermediate—β-form), complementary Nuclear Magnetic Resonance (NMR) techniques were applied. 1H Magic Angle Spinning NMR evidences the presence of different proton containing species in the interlayer slab depending on the hydration level. For α-form, HCa2Nb3O10·1.6H2O, 1H MAS NMR spectra reveal H3O+. Its molecular motion parameters were determined from 1H spin-lattice relaxation time in the rotating frame (T1ρ) using the Kohlrausch-Williams-Watts (KWW) correlation function with stretching exponent β = 0.28: eV, s. For the β-form, HCa2Nb3O10·0.8H2O, the only 1H NMR line is the result of an exchange between lattice and non-hydrogen-bonded water protons. T1ρ(1/T) indicates the presence of two characteristic points (224 and 176 K), at which proton dynamics change. The γ-form, HCa2Nb3O10·0.1H2O, contains bulk water and interlayer H+ in regular sites. 1H NMR spectra suggest two inequivalent cation positions. The parameters of the proton motion, found within the KWW model, are as follows: eV, s.

Crystal structure and dielectric properties of layered perovskite-like solid solutions Bi3−x Gdx TiTaO9 (x = 0.0, 0.1, 0.2, 0.3) with high Curie temperature

The Aurivillius phases [Bi2O2][A[Formula: see text][Formula: see text]O[Formula: see text]] are well-known ferroelectrics with high Curie temperatures [Formula: see text]. High-temperature piezoceramics Bi[Formula: see text][Formula: see text]TiTaO9 (BGdTTa, [Formula: see text]= 0.0, 0.1, 0.2, 0.3) were prepared by a solid-state reaction method. The structural and electrophysical characteristics of BGdTTa ceramics have been studied. According to the data of powder X-ray diffraction, all the compounds are single-phase with the structures of two-layer Aurivillius phases ([Formula: see text] = 2) with the orthorhombic crystal lattice (space group A21am). The temperature dependence of the relative permittivity [Formula: see text]/[Formula: see text] ([Formula: see text] of the compounds was measured and showed that the Curie temperature [Formula: see text] of perovskite-like oxides Bi[Formula: see text][Formula: see text]TiTaO9 increases linearly with an increase in the substitution parameter [Formula: see text] to [Formula: see text] = 925[Formula: see text]C. The activation energies of charge carriers have been found in different temperature ranges.

Exfoliation of Methylamine and n-Butylamine Derivatives of Layered Perovskite-Like Oxides HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) into Nanolayers

Exfoliation of Methylamine and n-Butylamine Derivatives of Layered Perovskite-Like Oxides HLnTiO4 and H2Ln2Ti3O10 (Ln = La, Nd) into Nanolayers

Synthesis and characterization of dense proton-conducting BaZr1-xYxO3 (x=0÷0.15) ceramics

In this paper, a technique for high-density BaZr1-xYxO3-6(x=0÷0.15) ceramics producing without the use of sintering additives is discussed. The obtained perovskite-like oxides are single-phase at the yttrium concentration of x=0÷0.1. For single-phase compounds, the lattice parameter increases when the yttrium addition rises. The microstructure of the produced samples was studied by scanning electron microscopy. Measurements of the thermal expansion and the total conductivity of BaZr1-xYxO3-8materials at different humidity evidence about the absence of phase transitions. The values of the specific conductivity depending on the temperature, the concentration of the acceptor impurity as well as the composition of the gas phase were implemented by the DC 4-probe method. In addition, the dependences of the effective activation energies on the conditions listed above are shown.

Phase transition at ambient pressure in complex oxide Sr3ScCoO6+δ. Morphotropic row Sr3ScMO7-δ (M = Ni–Cr)

A phase transition from a quasi-one-dimensional hexagonal structure (1D) to a two-dimensional layered structure (2D) of the second homolog of the Ruddlesden-Popper series was detected in the Sr3ScCoO6+δ complex oxide. The transition is unique since it occurs when the temperature increases without the use of high pressures and changes in the oxygen partial pressure. Using high-temperature X-ray diffraction and differential scanning calorimetry in situ, a transition temperature range 1296 ​K–1433 ​K was established. It is shown that in the quasi-one-dimensional phase the scandium and cobalt cations are ordered by prismatic and octahedral positions, while in the two-dimensional perovskite-like oxide they are statistically distributed by octahedral positions. Sr3ScCoO6+δ is the only compound in the Sr3ScMO7-δ (M ​= ​Ni - Cr) morphotropic series, which exists in two structural types. The 1D → 2D transformation is associated with the ability of cobalt to be in various combinations of oxidation states and spin states. The temperature dependence of the magnetic susceptibility of oxides of both types of structure in the Sr3ScMO7-δ (M ​= ​Ni - Cr) series is paramagnetic due to magnetic dilution with Sc ion. The tetragonal modification of Sr3ScCoO6+δ has a significantly larger magnetic moment compared to the hexagonal one.

Calcination Temperature Effect in Catalyst Reactivity for the CO SELOX Reaction Using Perovskite-like LaBO3 (B: Mn, Fe, Co, Ni) Oxides

H2 production by conventional processes such as reforming reactions involves formation of some undesired products such as CO. Selective CO oxidation (SELOX) is a good alternative to reduce its concentration because it is a thermodynamically favorable process. Perovskite-like oxides (LaMO3) are used in this work to catalyze the CO-SELOX process and they were synthetized by the self-combustion method. All catalysts were calcined at different temperatures (400 °C–800 °C) to analyze its impact on the material physicochemical properties. Different analytical techniques were used to study changes in structural and chemical properties. Temperature-programmed reaction (TPRe), using CO oxidation and CO-SELOX, was used to measure the catalytic reactivity of perovskite-like oxides. It was found that catalytic activity decreases when calcination temperature (CT) increases and that is correlated with oxygen mobility, surface defects, and surface concentration of manganese or cobalt species. It is also found that there is a crystalline phase change in the solids when the CT increases from 500 to 600 °C. The high catalytic activity observed at low CT remained even if they were calcined below 600 °C, which implies the possibility of amorphous species having catalytic activity that do not require a well-structured perovskite.

Oxygen vacancies-rich iron-based perovskite-like electrodes for symmetrical solid oxide fuel cells

Oxygen vacancies-rich iron-based perovskite-like oxides LaxSr3-xFe2O7-δ (x = 0, 0.25, 0.5) have been studied towards application as both anode and cathode materials for symmetrical solid oxide fuel cells (SSOFCs) at intermediate temperatures utilizing their excellent thermo-chemical structural stability. The conduction mechanism of LaxSr3-xFe2O7-δ was investigated according to the effect of La content on electrical conductivity and oxygen nonstoichiometry. Consequently, LaxSr3-xFe2O7-δ was used simultaneously as reversible symmetrical electrodes for YSZ electrolyte supported SSOFCs with GDC buffer layers. The maximum power density of LaxSr3-xFe2O7-δ-GDC symmetrical electrodes increased from 350 mW cm−2 to 480 mW cm−2 at 800 °C, and the corresponding cell polarization resistance decreased from 0.18 Ω cm2 to 0.16 Ω cm2, respectively. The enhanced performance is attributed to the improved electrical conductivity and electro-catalytic activity by the partial substitution of Sr with La. These results demonstrate that new iron-based perovskite-like oxides are promising for applications in intermediate temperatures SSOFCs.

Role of Oxygen in the Formation of Perovskite-Like Oxides of the BamBim+nOy Homologous Series (m = 1–9; n = 0–3, 5, 7, 9)

The effect of synthesis conditions on the phase composition and valence state of bismuth in perovskite-like oxides of the BamBim+nOy (m = 1–9; n = 0–3, 5, 7, 9) homologous series has been studied by means of X-ray diffraction and chemical analysis. The oxides synthesized at p(O2) = 1 kPa almost have not contained Bi(V), have been characterized by average oxidation number of bismuth $$\overline {{\rm{Bi}}} $$ = 3.00–3.01 and, consequently, have been stoichiometric in oxygen content. These phases have been thermodynamically stable from the crystallization region to 20°C. Under cooling below the solidus line, the BamBim+nOy oxides have been oxidized, as shown by increase in $$\overline {{\rm{Bi}}} $$ to above 3.06. The final oxidation products at ≈700–20°С have been ВаВiO3 and Ba4Bi1+33.00O23.5 oxides. Perovskite-like BamBim+nOy oxides with average oxidation number $$\overline {{\rm{Bi}}} $$ > 3.06 have not been found. At p(O2) = 21–100 kPa, individual oxides of this series which contain significant amount of Bi(V) or exclusively Bi(V) cannot be obtained.

Constructing perovskite-like oxide CsCa2Ta3O10: Yb, Er@Cs(PbxMn1-x)(ClyBr1-y)3 perovskite halide composites for five-dimensional anti-counterfeiting barcodes applications

Developing a secure and unclonable anti-counterfeiting technology with more dimensional encryptions is urgently demanded. All-inorganic halide perovskites hold great potential for applications in advanced fluorescence anti-counterfeiting owing to their superior optical properties, such as tunable emission colors, narrow emission peaks, etc. By further utilizing the feasibility of anion exchange for perovskite halides, this research successfully designs five-dimensional (5D) anti-counterfeiting barcodes with core–shell-like structured perovskite-like oxide and perovskite halide composites. The composites are prepared by a facile synthesis method, which includes adhesive growth of Cs(PbxMn1-x)(ClyBr1-y)3 on the surface of CsCa2Ta3O10: Yb, Er (abbreviated as CCTO: Yb, Er@CsMX3) via sharing Cs+ at the interface. The unique structure makes it possess sensitivity to some additive decrypted inks, offering one more intriguing anti-counterfeiting dimension beyond the common dual-mode fluorescence and time-gating technique. The CCTO: Yb, Er@CsMX3 composites exhibit typical green upconversion (UC) luminescence under a 980 nm laser, red or green or blue (RGB) emission under ultraviolet (UV) light irradiation, ns-ms emission decay time, and changeable emission color when treated with decrypted inks. The fluorescent inks and barcodes are simple for fabrication, efficient for coding, easy for viewing and difficult for cloning, making them promising for anti-counterfeiting applications.

Electrode materials based on complex d-metal oxides for symmetrical solid oxide fuel cells

The review addresses and highlights the main results of research on the physicohemical properties of single-phase and composite materials based on transition metal oxides in relation to their practical application as electrode materials for symmetrical solid oxide fuel cells. The electronic structures and thermodynamic stability of transition metal oxides with the perovskite structure are discussed. A detailed consideration is given to the thermal behaviour, chemical stability, electrical conductivity and electrochemical properties of a broad range of electrode materials based on iron-, chromium- and manganese-containing perovskite-like oxides and oxides that crystallize in other structure types. The analysis revealed the most promising compositions of electrode materials for symmetrical solid oxide fuel cells and effective approaches to the improvement of their functional characteristics.The bibliography includes 202 references.

Syngas conversion over perovskite-like LaCuxTi1-xO3/KIT-6 catalysts

The effect of the substitution of copper ions by titanium ions in LaCuxTi1-xO3 (x = 0.4–0.8) mixed oxide on physicochemical and catalytic properties in syngas conversion was studied. The activation and catalytic testing were accompanied by reduction of part of copper ions and destruction of the perovskite structure leading to the removal of titanium and copper cations. An increase in the titanium content leads to a decrease in the proportion of reduced copper with the preservation of the defective perovskite-like oxide substrate. The application of KIT-6 silica for increasing the surface area essentially enhanced catalytic efficiency of the system. The main product of syngas conversion was methanol; its formation selectivity on the synthesized mixed oxides is comparable to the selectivity on conventional CuZnAl oxide catalyst. With increasing copper content in the samples, the selectivity for higher alcohols increases and contribution of water-gas shift reaction to the total CO conversion rate grows.